SYNTHESIS OF ZEARALANES II AND RELATED COMPOUNDS AND INTERMEDIATES USEFUL IN THE SYNTHESES THEREOF

摘要

1391165 Lactones of 6-(hydroxy aiky)-# resorcylic acid COMMERCIAL SOLVENTS CORP 21 March 1973 [25 April 1972] 13667/73 Heading C2C Novel compounds I and II in which R is hydrogen or benzyl and X is an integer of 1 to 10 are prepared by a reaction sequence which for x = 10 (zearalane II) comprises reacting 10-undeeen-1-ol with p-toluenesulphonyl chloride to give the sulphonate ester which is treated with sodium bromide in methanol to produce l-bromo-10-undecene; this is subjected to a Grignard reaction with triethyl orthoformate to form ll-dodecenal which on reaction with malonic acid gives trans-2,13- tetra decanoic acid; this acid is esterified with diazomethane to give the methyl ester which on treatment with ethyl acetoacetate in the presence of sodium ethoxide yields the sodium salt of ethyl-6-(10-undecenyl)-#-dihydroresorcylate which is brominated at the 3-position and treated with sodium ethoxide and sulphuric acid to give ethyl 6- ( 10-undecenyl)-#-resorcylate which is reacted with benzyl chloride to form the corresponding dibenzyl ether; the ether is subjected to diborane, water, sodium acetate and hydrogen peroxide to yield ethyl 2,4-bis(benzyloxy) -6-( 11 -hydroicy undecyl)-benzoate which on reaction with sodium ethoxide undergoes ring closure to form the Á-lactone XX and the dilactone XXA in which x = 10, which may be debenzylated by hydrogenation. Norecaralane II (x = 8) and the corresponding dimeric dilactone are prepared similarly starting from 10-undecenal. The dimeric dilactone of 2,4-bis-(benzyloxy)-6-(5- hydroxy pentyl)-benzoic acid (x = 4) is similarly prepared from 5-hexenal which is prepared by heating 3-hydroxy- 1 ,5-hexadiene. Compounds I and II are useful anabolic agents in the production of animals, and may be administered directly or in fixed compositions, orally, parenterally or subcutaneously.